Random copolymer

Abstract

A random copolymer comprising ethylene, a 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and optionally an alpha-olefin having at least three carbon atoms or cycloolefin. The mole ratio of polymerized units from the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units from ethylene is from 3:97 to 95:5 and the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene is incorporated in the polymer chain as polymerized units without ring-opening. The copolymer is prepared by copolymerizing ethylene with the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene in a hydrocarbon medium in the presence of a catalyst formed from a vanadium compound and an organoaluminum compound which are soluble in the hydrocarbon medium. The copolymer has excellent transparency and a well balanced combination of heat resistance, heat aging resistance, chemical and solvent resistance, dielectric properties and mechanical properties such as rigidity.

What is claimed is: 
     
       1. A novel random copolymer, characterized in that (A) it comprises ethylene and a 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene represented by the following formula (1) ##STR28##  wherein R 1  and R 2  are identical and different and each represents a hydrogen atom, a halogen atom or an alkyl group, or R 1  and R 2  may be bonded to each other to form a trimethylene group or a group represented by the following formula ##STR29##  in which R 3  and R 4  are identical or different and each represents a hydrogen atom, a halogen atom or an alkyl group,   (B) the mole ratio of polymerized units derived from 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units derived from ethylene is from 3:97 to 95:5, and   (C) the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene is incorporated in the polymer chain as polymerized units represented by the following formula (2) ##STR30## wherein R 1  and R 2  are as defined above.   
     
     
       2. The random copolymer of claim 1 which has an intrinsic viscosity, measured in decalin at 135° C., of 0.005 to 20 dl/g. 
     
     
       3. The random copolymer of claim 1 wherein in formula (1), at least one of R 1  and R 2  is an alkyl group. 
     
     
       4. A novel random copolymer, characterized in that (A) it comprises at least one 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene of the following formula (1) ##STR31##  wherein R 1  and R 2  are identical and different and each represents a hydrogen atom, a halogen atom or an alkyl group, or R 1  and R 2  may be bonded to each other to form a trimethylene group or a group represented by the following formula ##STR32##  in which R 3  and R 4  are identical or different and each represents a hydrogen atom, a halogen atom or an alkyl group, ethylene and at least one compound selected from the group consisting of alpha-olefins having at least 3 carbon atoms and cycloolefins,     (B) the mole ratio of polymerized units from the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units from ethylene is from 3:97 to 95:5,   (B') the mole ratio of polymerized units from at least one compound selected from the group consisting of alpha-olefins having at least 3 carbon atoms and cycloolefins to the polymerized units from the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene is from 95:5 to 20:80, and   (C) the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene is incorporated in the polymer chain as polymerized units represented by the following formula (2) ##STR33##  wherein R 1  and R 2  are as defined hereinabove.   
     
     
       5. The random copolymer of claim 4 which has an intrinsic viscosity, measured in decalin at 135° C., of 0.005 to 20 dl/g. 
     
     
       6. The random copolymer of claim 4 wherein at least one of R 1  and R 2  is an alkyl group. 
     
     
       7. A process for producing a random copolymer comprising ethylene and a 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene represented by the following formula (1) ##STR34##  wherein R 1  and R 2  are identical and different and each represents a hydrogen atom, a halogen atom or an alkyl group, or R 1  and R 2  may be bonded to each other to form a trimethylene group or a group represented by the following formula ##STR35##  in which R 3  and R 4  are identical or different and each represents a hydrogen atom, a halogen atom or an alkyl group, the mole ratio of polymerized units derived from 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units derived from ethylene being from 3:97 to 95:5, and the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene being incorporated in the polymer chain as polymerized units represented by the following formula (2) ##STR36## wherein R 1  and R 2  are as defined above; which comprises copolymerizing ethylene with said 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene in a hydrocarbon medium in the presence of a catalyst formed from a vanadium compound and an organoaluminum compound which are soluble in the hydrocarbon medium.   
     
     
       8. The process of claim 7 wherein the random copolymer has an intrinsic viscosity, measured in decalin at 135° C., of 0.005 to 20 dl/g. 
     
     
       9. The process of claim 7 wherein in formula (1), at least one of R 1  and R 2  is an alkyl group. 
     
     
       10. The random copolymer of claim 1 wherein the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene of formula (1) is selected from the group consisting of 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene 2-decyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 12-ethyl-hexacyclo[6,6,1,1 3 ,6,1 10 ,13,0 2 ,7,0 9 ,14 -heptadecene-4, 12-methyl-hexacyclo[6,6,1,1 3 ,6,1 10 ,13,0 2 ,7,0 9 ,14 ]-heptadecene-4, 12-isobutyl-hexacyclo-6,6,1,1 3 ,6,1 10 ,13,0 2 ,7,0 9 ,14 ]-heptadecene-4, hexacyclo[6,6,1,1 3 ,6,1 10 ,13,0 2 ,7,0 9 ,14 ]heptadecene-4, pentacyclo[6,5,1,1 3 ,6,0 2 ,7, 9 ,13 ]pentadecene-4 and mixtures thereof. 
     
     
       11. The random copolymer of claim 3 wherein the alkyl group has from 1 to 10 carbon atoms. 
     
     
       12. The random copolymer of claim 1 wherein the mole ratio of polymerized units derived from 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units derived from ethylene is from 5:95 to 80:20. 
     
     
       13. The random copolymer of claim 1 wherein the mole ratio of polymerized units derived from 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to polymerized units derived from ethylene is from 10:90 to 80:20. 
     
     
       14. The random copolymer of claim 2 wherein the intrinsic viscosity is from 0.01 to 15 dl/g. 
     
     
       15. The random copolymer of claim 1 in which the mole ratio of the polymerized units from the 1,4,5,8a-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to the polymerized units from ethylene is from 10:90 to 90:10, said copolymer having an intrinsic viscosity, measured in decalin at 135° C., of 0.3 to 15 dl/g, a crystallinity, determined by X-ray diffraction, of not more than 25%, a melting point, measured by a differential scanning calorimeter, of not more than 128° C., and a glass transition temperature measured by a dynamic mechanical analyzer of at least 80° C. 
     
     
       16. The random copolymer of claim 15 wherein the mole ratio is from 15:85 to 80:20, the intrinsic viscosity is from 0.5 to 10 dl/g, the crystallinity is not more than 10%, the melting point is not more than 100° C., and the glass transition temperature is from 100° to 220° C. 
     
     
       17. The random copolymer of claim 1 in which the mole ratio of the polymerized units from the 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to the polymerized units from ethylene is from 10:90 to 90:10, said copolymer having an intrinsic viscosity, measured in decalin at 135° C., of 0.05 to 0.3 dl/g, a crystallinity, determined by X-ray diffraction, of not more than 25%, a melting point, measured by a differential scanning calorimeter, of not more than 128° C., a glass transition temperature measured by a dynamic mechanical analyzer of at least 80° C., and a viscosity at 180° C. of 100 to 2×10 5  centipoises. 
     
     
       18. The random copolymer of claim 17 wherein the mole ratio is from 15:85 to 80:20, the intrinsic viscosity is from 0.01 to 0.3 dl/g, the crystallinity is not more than 10%, the melting point is not more than 100° C., the glass transition temperature is from 100 to 220° C., and the viscosity is from 100 to 2×10 4  centipoises. 
     
     
       19. The random copolymer of claim 1 in which the mole ratio of the polymerized units from the 1,4,5,8a-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphytalene to the polymerized units from ethylene is from 3:97 to 20:80, and the copolymer has an intrinsic viscosity, measured in decalin at 135° C., of 0.3 to 20 dl/g, a crystallinity, determined by X-ray diffraction, of not more than 10%, a melting point, measured by a differential scanning calorimeter, of not more than 128° C., and a glass transition temperature, measured by a dynamic mechanical analyzer of 25° to 100° C. 
     
     
       20. The random copolymer of claim 19 in which the mole ratio is from 5:95 to 10:90, the intrinsic viscosity is from 1.0 to 20 dl/g, the crystallinity is not more than 5%, the melting point is not more than 100° C., and the glass transition temperature is from 30° to 80° C. 
     
     
       21. The random copolmer of claim 4 which comprises an alpha-olefin having from 3 to 12 carbon atoms. 
     
     
       22. The random copolymer of claim 4 which comprises a cycloolefin selected from the group consisting of cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, styrene, alpha-methylstyrene, norbornene, methylnorbornene, ethylnorbornene, isobutylnorbornene, 2,3,3a,7a-tetrahydro-4,7-methano-1H-indene and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene. 
     
     
       23. The random copolymer of claim 4 which comprises a cycloolefin selected from the group consisting of norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, and 5-isobutyl-2-norbornene. 
     
     
       24. The random copolymer of claim 5 which has an iodine number of not more than 5, a crystallinity of not more than 40%, a melting point, determined by a differential scanning calorimeter, of not more than 135° C., a glass transition temperature of at least 2° C., a heat decomposition temperature in the range of from 350° to 420° C., a flexular modulus in the range of 1×10 4  to 3×10 4  kg/cm 2 , a flexular yield strength of from 300 to 1500 kg/cm 2 , a density of at least about 0.86 g/cm 3 , a refractive index of 1.47 to 1.58, a dielectric constant of 1.5 to 4.0 and a dielectric tangent of 5×10 -3  to 5×10 -5 .